Priming mixture



Patented Oct. 11, 1933- UNITED STATES PATENT OFFIGE rnnvmve MIXTURE Joseph D. McNutt, New Haven, Conn., assignor to Winchester Repeating Arms Company, New Haven, Conn, a corporation of Maryland No Drawing. Application March 10, 1933 i Serial N0. 660,236.

even though considerable effort has been made to eliminate mercury fulminate from priming mixtures. While it possesses certain advantages, it also possesses certain disadvantages. ,Amalgama tion of the cartridge cases caused by the free mercury produced by the decompositionof the mercury fulmlnat'e when the cartridge is exploded prevents reloading of center fire cartridges. By employing a priming mixture in which no mercuryfulminate. is present, this amalgamation is limited and this permits reloading and reuse of center fire cartridge cases. The priming mixture of my invention alsopossesses advantages for use in rim fire primers. It has greater stability on storing and therefore permits the ammunition to be used and better results obtained after it has been stored for long periods ,o'fv time.

In the present inventiorLI employ a salt of tetrazene. The term tetrazene is used in the ammunition industry to designate a-material that is also designated by the term guanylnitroso- 'amino-guanyltetrazene although it must be recognized' that tetrazene is the genusof which the alleged synonym is but one of a score of species. I am aware that it has been proposed to employ .tetrazole derivatives and salts of tetrazole derivatives in the manufacture of priming mixtures for small arms ammunition. It hasalso beenproposed to employ tetrazene as aningredient of a priming mixture. The invention forming the subject matter of the present application differs from these priorproposals in that I employ a metallic salt of tetrazene, preferably a salt of a heavy metal. The tetrazene salts which I have found particularly useful arethe silver; salt of tetrazene and the cuprous salt of tetrazene. I prefer.-

with lead dinitrophenylazide. These materials ii aw 1;

may be used in the following proportions with the usual oxidizing, reducing and abrasive agents in the manufacture of priming mixtures 'the manner well known to those skilled in th'e'art. The heavy metalsalts'fof tetrazene'may'be' prepared-by substantially following the method 'disiclosedby Leihig: Annalen der ChemieilQll);

Vol; 380, pp. 138-, 139, 140, for the-preparation of a silversaltof tetrazene. A specificexample of my method of preparing-a, silver salt of tetrazene isasfollows: K r:

- grams of tetrazene is dissolved int-100cc; of

38% nitric acid maintaining a temperature be tween 40 and .50? C, To this isadded130grams silver nitrate dissolved in 250 cc.1;of-water,;the solution being thoroughly agitated until the precipitation ofgthe silver salt of tetrazeneiscomplete. During the addition of the silver nitrate solution the temperature is kept-also betweenll and 50 C. The precipitate is thoroughly washed and dried and is then ready-'for-use, ,4 Thesilver salt oftetrazene referredto :above AgC2H7ON1oAgNOa.3H20.w I i In the preparation of a cuprous salt of tetrazene substantially the same method "is" followed, cuprous chloride being substituted for" silver is the double salt and has the'rziormula-snitrate'and the proportions being followed to'ob- '1 tain the proper amount of copper for combination with the tetrazene. r

Lead dinitrophenylazide may be p'repared'by dissolving 100 grams of diazodinitrophenoll' in 1200 cc; of acetone. v'I'o this solutionjfthenadd a solution consisting of 30 grams of'sodiurn azide dissolved in 300 cc. of water. Theheat of the solution should be maintained'below' 50 C; The addition of the sodium azide solution causes a reaction resulting in the; formation 'of sodium dinitrophenylazide. I then add grams of lead nitrate dissolved in 900 'cc. of water. The solution is-then cooled; to 15 C. and lead dinitrophenylazide is precipitated. The precipitate is washed with water and alcohol until it is free of lead nitrate. The formula for the material lead dinitrophenylazide is PbCizNioOio. p, ably employasalt of tetrazene in combination The, reactions which occur are represented by :the following structural equations:

r a 2 l1ydrox -3, 5,- nitrobenzene diazodi-nitrop enyl mum aside. Bzide.

- Normal lead salt of 2-hydroxy-3, 5, -dinitrophenylazide:

0'Na Pb-0 A suitable priming mixture for center fire cartridges may be formed by mixing the following ingredients in substantially the following proportions:

Lead Peroxide 10 to 25%, preferably 17% AntimonySulphide 15 to 25%, preferably 22% Calcium Silicide 0 to 10%, preferably 7% The proportions of these ingredients may, of course,-be varied depending upon the commercial strength of the ingredients and to meet the requirements of various uses of the mixture.

The ingredients are first thoroughly and homogeneously mixed and then poured into individual pellets of the'proper size for the individualcharges in the'customary way, by means of a charge plate provided with perforations adapted to mold pellets of the proper size.- These pellets are then loaded into primer cups in the usual way and the primer cups then assembled in the cartridge cases. 1

These materials may also be employed in rim fire-mixtures, A suitable priming mixture for rim fire use may be formed bymixing the following ingredients in the following proportions:-

Lead Dinitrophenyl- 1 azide 15 to 25%;.Preferably 20% Silver Salt of Tetrazene 15 to 25%, preferably 20% Lead Dinitroxybenzoic AoidPbCf'zHaN'zor 8to15% ,preferably 12% Lead Peroxide .benzoic acid is as follows:

Barium Nitrate 15 to 25%. preferably 18% 5 to 10%, preferably 8% Ground Glass 20 to 25%, Preferably 22% The structural formula for lead dinitro-oxy As in the center fire mixtures the proportions of the ingredients may be varied depending upon the properties desired inthe individual case and the commercial strength of the ingredients. The rim fire mixture is prepared in the usual way, poured into individual pelletsof the proper size for the individual charges by means of a charge plate in the usual-manner and then transferred toempty rim fire cartridge shells. The priming mixture is then forced to distribute itself into the hollow rim of the cartridge shell by spinning the shell in the customary machine. The shells are then loaded with powder and bullets in the customary way. Priming mixtures may also be prepared containing salts of tetrazene and lead azide. Thus a rim fire mixture may consist of +2NaNOa the following ingredients in substantially the following proportions: Lead Azide 15 to 25%, preferably 23% Glass 15 to 25%, preferably 21% Lead Peroxide 6 to 10%, preferably 8% Calcium Silicide -12 to 20%, preferably 16% Silver Salt of Tetrazene 3 to 10%, preferably 7% Barium Nitrate 18 to 30%, preferably 22% Gum 2to 4%,preferably 3% Likewise, a center fire mix ture may be formed of the following ingredients in substantially the following proportions: 1

Lead Azide 12 to 20%, preferably 16% Lead Peroxide 12 to 20%, preferably 15% Calcium Silicide -12 to 20% preferably 15% Silver Salt of Tetrazene 2to 10%, preferably 5% Barium Nitrate -28to 35 preferably 32% Gum 2t0 4%,preferably 3% Antimony Sulphide l() to 18%, preferably 14% This application is a continuation in part of my copending application Serial No. 636,681,'filed October 7, 1932.

I claim:

1. A priming mixture comprising a heavy metal salt of tetrazene.

2. A priming mixture comprising silver salt of tetrazene.

3. A priming mixture comprising cuprous salt of tetrazene.

4. A priming mixture comprising a heavy metal salt of tetrazene and lead dinitrophenylazide.

5. A priming mixture comprising silver saltof ll5 tetrazene and lead dinitrophenylazide.

6. Aprimingmixture comprising cuprous salt of tetrazeneand lead dinitrophenylazide.

7. A priming mixture comprising silver salt of tetrazene, lead dinitrophenylazide, an oxidizing agentand a fuel.

8. A priming mixture comprising cuprous salt of tetrazene, lead dinitrophenylazide, an oxidizing agent and a fuel.

9. A priming mixture comprising from 15 to 20 percent lead dinitrophenylazide, 7 to 12 percent silver salt of tetrazene, 17 to 35 percent barium nitrate, 10 to 25 percent lead peroxide, 15 to 25 percent antimony sulphide, and 0 to 10 percent calcium silicide.

10. A priming mixture comprising substantially 17 percent lead dinitrophenylazide, substantially percent silver salt of tetrazene, substantially 27 percent barium nitrate, substantially 17 percent lead peroxide, substantially 22 percent antimony sulphide and substantially 7 percent calcium silicide.

11. A priming mixture comprising from 15 to 25 percent lead dinitrophenylazide, 15 to 25 percent silver salt of tetrazene, 8 to 15 percent lead dinitrooxybenzoic acid, 15 to 25 percent barium nitrate, 5 to 10 percent lead peroxide and 20 to 25 percent ground glass.

12. A priming mixture comprising substantially 20 percent lead dinitrophenylazide, substantially 20 percent silver salt of. tetrazene, substantially 12 percent lead dinitrooxybenzoic acid, substantially 18 percent barium nitrate, substantially 8 percent lead peroxide and substantially 22 percent ground glass,

13. A priming mixture comprising a heavy metal salt of tetrazene and lead azide.

14. A priming mixture comprising a silver salt of tetrazene and'lead azide. i 15. A priming mixture comprising a cuprous salt of tetrazene and lead azide.

16. A priming mixture comprising a silver salt of tetrazene, lead azlde, and oxidizing agent and a fuel. v

17. A priming mixture comprising a cuprous salt or tetrazene, lead" azide, and oxidizing agent and a fuel.

18. A priming mixture comprising from to percent lead azide, 18 to 25 percent glass, 6 to 10 percent lead peroxide, 12 to 20 percent calcium silicide, 3.to 10 percent silver salt of tetrazene, 18 to percent barium nitrate and 2 to 4 percent gum. V

19. A priming mixture comprising substantially go 23 percent lead azide, substantially 21 percent glass, substantially 6 percent lead peroxide, substantially 16 percent calcium silicide, substantially 7 percent silver salt of tetrazene, substantially 22 percent barium nitrate and substantially 3 percent gum.

20. A priming mixture comprising from 12 to 20 per cent lead azide, 12 to 20 percent lead peroxide, 12 to 20 percent calcium silicide, 2 to 10 percent silver salt of tetrazene, 28 to percent barium nitrate, 2 to 4 percent gum and 10 to 18 percent antimony sulphide.

21. A priming mixture comprising substantially 16 percent lead azide, substantially 15 percent lead peroxide, substantially 15 percent calcium silicide, substantially 5 percent silver salt of tetrazene, substantially 32 percent barium nitrate, substantially 3 percent gum and substantially 14 percent antimony sulphide.

JOSEPH n. MCNUTI. 95

CERTIFICATE OF CORRECTION.

Patent No. 1,930,653.

October 17, 1933.

' JOSEPH u. McNU'lT.

it is hereby, certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, line 132, claim 10, after "substantially" insert thenumber 10; and that the said Letters Patent should be read withthis correction therein that the same may conform to the record of the case in the PatentfOifice.

Signed and sealed this 28th day oi November, A, D, 1933,

(Seal) F. M. Hopkins Acting Commissioner of Patenta. 

